Substituted ether or thioether isothiazole azo dyes

ABSTRACT

Disclosed are novel azo dyes containing an isothiazole moiety substituted with ether or thioether groups. The dyes produce orange to violet shades on hydrophobic texture fiber including polyesters, polyamides, and cellulose esters and have excellent fastness properties including lightfastness, washfastness and resistance to sublimation. The dyes have the general formula ##STR1## R is lower alkyl or phenyl; X is O or S; R 1  is lower alkyl or substituted lower alkyl, cyclohexyl, phenyl or substituted phenyl; and when X is S, R 1  can be various heterocycles such as pyridyl, pryimidinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl and azolyl radicals; 
     R 2  is hydrogen, lower alkyl, lower alkoxy, or acylamido; 
     R 3  is H, lower alkyl, or lower alkoxy; and R 4  and R 5  are selected from 1 to 2 of H, alkyl of 1-8 carbons, substituted alkyls, cyclohexyl, phenyl or substituted phenyl.

This is a continuation of application Ser. No. 966,173, filed Dec. 4,1978, now abandoned.

This invention relates to novel azo dyes containing an isothiazolemoiety substituted with ether or thioether groups. The dyes produceorange to violet shades on hydrophobic texture fiber includingpolyesters, polyamides, and cellulose esters and have excellent fastnessproperties including lightfastness, washfastness and resistance tosublimation.

The dyes of this invention have the following general formula: ##STR2##wherein R is lower alkyl or phenyl; X is O or S; R₁ is lower alkyl orlower alkyl substituted with 1-3 of --OH, Cl, Br, aryl, aryloxy, loweralkanoyloxy, or lower alkoxy which also may be substituted with --OH,Cl, Br, or lower alkoxy; cyclohexyl; phenyl; phenyl substituted with Cl,Br, lower alkoxy, or lower alkyl; and when X is S, R₁ can be a radicalselected from pyridyl, pryimidinyl, benzothiazolyl, benzoxazolyl,benzimidazolyl, azolyl radicals having the formula ##STR3## wherein Y isan oxygen or sulfur atom and Z is an ethylenically unsaturated, two atomchain of carbon atoms, or of a nitrogen and a carbon atom, wherein anyof said azolyl radicals may be substituted with lower alkyl, phenyl, orphenyl substituted as in R₁ above; R₂ is hydrogen, lower alkyl, loweralkoxy, or acylamido where the acyl moiety is selected from formyl;lower alkoxycarbonyl; lower alkanoyl which also may be substituted withcyano, lower alkoxy, lower alkoxycarbonyl, phenoxy, or phenyl; aroylwhich also may be substituted with halogen; cycloalkylcarbonyl; andlower alkylsulfonyl; R₃ is H, lower alkyl, or lower alkoxy; and R₄ andR₅ are selected from 1 or 2 of H; alkyl of 1-8 carbons; cyclohexyl;phenyl; phenylsubstituted with lower alkoxycarbonyl; and lower alkylsubstituted with cyclohexyl, lower alkanoyloxy, lower alkoxycarbonyl,succinimido, lower alkanoylamido, lower alkylsulfonylamido, sulfamoyl,carbamoyl, lower alkyl sulfonyl, hydroxy, pyrrolidono, phthalimido,aryl, cyano, aryloxy, lower alkoxy carbonyloxy, lower alkoxy, phenoxy,and lower alkoxyalkoxy.

Typical of the azolyl radicals are thiazol-2-yl; oxazol-2-yl;1,3,4-thiadiazol-2-yl; 1,3,4-oxadiazol-2-yl; 1,2,4-thiadiazol-5-yl; andbenzothiazol-2-yl.

The dyes of the present invention are prepared by the following generalmethod: ##STR4##

The preparation of compounds I is given in British Pat. No. 1,379,233. Atypical preparation is as follows: 1.59 parts of3-methyl-4-nitro-5-aminoisothiazole are stirred with a solution of 20parts of acetic acid, 3.0 parts of concentrated hydrochloric acid and 15parts of water. The mixture is cooled to 10°-15° C. To this is added0.69 parts of sodium nitrite in 5 parts of water. The resultant diazosolution is filtered and the filtrate added to a solution of 1.32 partsof N,N-dimethylaniline in 50 parts of water and 1.5 parts ofconcentrated hydrochloric acid cooled to 0°-5° C. The resultant dyestuffis isolated by filtration after adjustment of the pH to 4.0 with sodiumacetate. After washing with water the dyestuff is dried at 40° C. undervacuum.

The dyestuff corresponds to the formula ##STR5## During this preparationthe nitro group is replaced by a chlorine atom from the hydrochloricacid. If sulfuric acid is used instead of hydrochloric acid, the nitrogroup remains intact. The same dyestuff can be obtained by commencingwith the corresponding 4-chloroisothiazole. It has been found that thehalogen atom in the isothiazole nucleus is labile and can be replaced byanions such as R₁ X⁻ wherein R₁ and X are defined above. In the reactiona catalytic amount of cuprous bromide is employed, and the reactions ingeneral are carried out in N,N-dimethylformamide, but other solvents maybe employed.

The anion of the mercaptan or hydroxyl derivative need not be preformed,but may be formed in situ by using the R₁ XH compound plus a basecapable of forming the salt. Potassium carbonate and sodium carbonateare acceptable bases for this reaction.

The followiing examples will illustrate further the preparation of thedyes of this invention.

EXAMPLE 1 Reaction of Bromo Dye with 2-Mercaptobenzothiazole

A mixture of3-acetamido-4-(4-bromo-3-methylisothiazol-5-ylazo)-N,N-diethylaniline(1.0 g), 2-mercaptobenzothiazole (0.84 g), potassium carbonate (0.70 g),N,N-dimethylformamide, and a trace of cuprous bromide was heated at135°-140° C. for one hour. Thin-layer chromatography showed that thereaction was complete. The reaction mixture was cooled, drowned into 200ml water, the dye collected by filtration, washed with water, and driedin air. The dye produced bright red shades on polyester fabrics and hadthe following structure: ##STR6##

EXAMPLE 2

The bromo intermediate of Example 1 (1.0 g) was reacted with3-mercapto-1(H)-1,2,4-triazole (0.5 g) exactly as described in Example 1to yield the following dye: ##STR7##

This dye produced bright red shades on polyamide, cellulose ester, andpolyester fibers and had excellent fastness properties.

EXAMPLE 3 Reaction of Bromo Dye with Alkyl Mercaptan

A mixture of the bromo dye in Example 1 (1.0 g), 2-mercaptoethanol (0.4g), potassium carbonate (0.7 g), and a trace of cuprous bromide washeated at 100° C. for 45 minutes. Thin-layer chromatography showedcomplete reaction. The product was isolated by drowning the reactionmixture into water, collecting the dye by filtration, washing with waterand drying in air. The dye had the following structure: ##STR8##

EXAMPLE 4 Acetylation of Dye in Example 3

A mixture of hydroxy dye of Example 3 (0.3 g), acetic acid (4 ml), andacetic anhydride (1 ml) was heated at 90°-95° C. for one hour. Thereaction mixture was drowned into water (25 ml) and the product isolatedby filtrating. The dye was washed with water and dried in air and hadthe following structure: ##STR9##

EXAMPLE 5 Reaction of Bromo Dye with Phenol

The bromo dye of Example 1 (1.0 g), phenol (0.5 g), potassium carbonate(0.7 g), N,N-dimethylformamide, and a trace of cuprous bromide weremixed and heated at 110°-115° C. for 45 minutes. The reaction wasessentially complete as evidenced by thin-layer chromatography. The dyewas isolated by drowning into water, filtering, drying and thenrecrystallizing from 50 ml of denatured alcohol. The structure of thedye was ##STR10## and when applied to polyamide and polyester fibersproduced bright scarlet shades having excellent fastness properties.

The dyes in the following tables are generally prepared by the aboveprocedures.

    TABLE 1      ##STR11##      Example R R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 Color      6 CH.sub.3 C.sub.6 H.sub.5 NHCOCH.sub.3 H C.sub.2 H.sub.5 C.sub.2     H.sub.5 Bluish-Red 7 " C.sub.6 H.sub.4p-Cl NHCOC.sub.2 H.sub.5 " C.sub.3     H.sub.7n C.sub.3 H.sub.7n " 8 " C.sub.6      H.sub.4p-CH.sub.3 NHCOCH(CH.sub.3).sub.2 " C.sub.2 H.sub.5 CH.sub.2     C.sub.6 H.sub.5 " 9 " C.sub.6 H.sub.4o-Cl NHCOCH.sub.3 " C.sub.2 H.sub.5     C.sub.6 H.sub. 11 " 10 " C.sub.6 H.sub.11 " " " CH.sub.2 C.sub.6     H.sub.11 " 11 " C.sub.2 H.sub.5 " " " CH.sub.2 CH(CH.sub.3).sub.2 12 "     C.sub.4 H.sub.9n NHCOC.sub.6 H.sub.5 " " CH.sub.2 CH.sub.2 C.sub.6     H.sub.5 " 13 " CH.sub.2 COOC.sub.2 H.sub.5 NHCOC.sub.6 H.sub.11 " "     C.sub.2 H.sub.5 " 14 " CH.sub.2 CH(OH)CH.sub.2 OH NHCOC.sub.6 H.sub.4oCl     " " " " 15 " CH.sub.2 CH.sub.2 Cl NHCOH " " " " 16 " CH.sub.2 C.sub.6     H.sub.5 NHCOCH.sub.2 CN " " " " 17 " CH.sub.2 C.sub.6 H.sub.4p-Cl     NHCOCH.sub.2 OCH.sub.3 " " CH.sub.2 CH(OH)CH.sub.3 "      18 "     ##STR12##      " " " CH.sub.2 CH.sub.2 CN Red  19 " " " " CH.sub.2 CH.sub.2      OCOCH.sub.3 C.sub.2 H.sub.5 Bluish-Red 20 " " CH.sub.3 " C.sub.2     H.sub.5 C.sub.2 H.sub.4 CN Red      21 " " " "     ##STR13##      C.sub.2 H.sub.5 Red  22 " " H " C.sub.2 H.sub.5 C.sub.2 H.sub.4 CN     Scarlet 23 " " CH.sub.3 " CH.sub.2 CH.sub.2 NHCOCH.sub.3 C.sub.2 H.sub.5     Red 24 " " " " CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3 " " 25 " " " "     CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2 " " 26 " " " " CH.sub.2 CH.sub.2     CONH.sub.2 " " 27 " " " " CH.sub.2 CH.sub.2 COOCH.sub.3 " " 28 " " " "     CH.sub.2 CH.sub.2 OH CH.sub.2 C.sub.6 H.sub.5 "      29 "     ##STR14##      NHCOCH.sub.3 " C.sub.2 H.sub.5 C.sub.2 H.sub.5 Bluish-Red  30 " " "     OCH.sub.3 " " Violet 31 " " " CH.sub.3 H CH.sub.2 CH.sub.3 Red 32 " " "     " " CHCH(CH.sub.3)C.sub.2 H.sub.5 Red 33 " " " " " CH.sub.2 CH.sub.2 CN     "      34 "     ##STR15##      " " " CH.sub.2 CH(CH.sub.3)CO.sub.2 C.sub. 2 H.sub.5 "  35 " " " " "     CH.sub.2 CH(CH.sub.3)C.sub.4 H.sub.9n " 36 " " " OCH.sub.3 C.sub.2     H.sub.5 C.sub.2 H.sub.5 Violet 37 " " " " H CH.sub.2 CH(CH.sub.3)C.sub.4     H.sub.9n "      38 "     ##STR16##      NHCO.sub.2 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 " Bluish-Red  39 "      ##STR17##      NHCOCH.sub.3 " " CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 "  40 "      ##STR18##      " " " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 "      41 "     ##STR19##      " " " (CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5      42 "     ##STR20##      " " " CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 "      43 "     ##STR21##      " " " CH.sub.2 C.sub.6 H.sub.4p-COOCH.sub.3 "      44 "     ##STR22##      " " " CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.3 "      45 "     ##STR23##      " " "      ##STR24##      "  46 " C.sub.6 H.sub. 4p-C(CH.sub.3).sub.3 " " " CH.sub.3 " 47 " "     OCH.sub.3 " " C.sub.2      H.sub.5 " 48 " " " CH.sub.3 " H " 49 " " NHSO.sub.2 CH.sub.3 H "     C.sub.2 H.sub.5 " 50 " " NHCOCH.sub.2 OC.sub.6 H.sub.5 " " " " 51 " "     NHCOCH.sub.2 C.sub.6 H.sub.5 " " " " 52 " " NHCOCH.sub.2 CH.sub.2     CO.sub.2 CH.sub.3 " " " "      53 " " NHCOCH.sub.3 "     ##STR25##      " "      54 " " " "     ##STR26##      " "  55 " " OCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Violet     56 C.sub.6 H.sub.5 " NHCOCH.sub.3 H " " Bluish-Red      57 "     ##STR27##      " " " " "  58 " CH.sub.2 CH.sub.2 OH " " " " " 59 " CH.sub.2 CH.sub.2     OCH.sub.3 " " " " "      60 "     ##STR28##      " " " " "  61 CH.sub.3 C.sub.6 H.sub.5 NHCOCH.sub.3 H CH.sub.2 CH.sub.3     CH.sub.2 C.sub.6 H.sub.5 Scarlet 62 " C.sub.6 H.sub.4p-Cl " " " CH.sub.2     CH.sub.2 CH.sub.3 " 63 " C.sub.6 H.sub. 4o-Cl " " CH.sub.2 C.sub.6     H.sub.11 C.sub.2 H.sub.5 " 64 " C.sub.6 H.sub.4m-CH.sub.3 " " C.sub.6     H.sub.11 " " 65 " C.sub.6 H.sub.4p-OCH.sub.3 " " CH.sub.2 CH.sub.2     C.sub.6 H.sub.5 " " 66 C.sub.6 H.sub.5 C.sub.6 H.sub.4p-C.sub.6 H.sub.11     " " C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 67 CH.sub.3 C.sub.6      H.sub.4o-CH.sub.3 " " C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3)C.sub.2     H.sub.5 " 68 " C.sub.6 H.sub.4p-C.sub.6 H.sub.5 " " " " " 69 " C.sub.6     H.sub.4p-OCH.sub.2 CH.sub.2 OH " " " " " 70 " C.sub.6 H.sub.5 " " "     CH.sub.2 CH.sub.2 CN Orange 71 " C.sub.6 H.sub.5 CH.sub.3 " " " " 72 " "     " " " " " 73 " " " " " CH.sub.2 CH.sub.2 OCOCH.sub.3 " 74 " " " "     CH.sub.2 CH.sub.2 CN " " 75 " " H " " CH.sub.2 CH.sub.3 "  76 " " " "      ##STR29##      CH.sub.2 C.sub.6 H.sub.5 "  77 " " CH.sub.3 CH.sub.3 H CH.sub.2     CH.sub.2 CN " 78 " " " " " CH.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3 " 79 "     " " OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Scarlet 80 " " OCH.sub.3     CH.sub.3 " " " 81 " " NHCOCH.sub.3 OCH.sub.3 " " Red 82 " " " " H     CH.sub.2 CH(CH.sub.3)C.sub.4 H.sub.9n "  83 " " " " " C.sub.6 H.sub.11 "     84 " " " " CH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 " 85 " " NHCOC.sub.6     H.sub.5 H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 Scarlet 86 " " NHCOC.sub.2     H.sub.5 " CH.sub.2 CH.sub.2 NHCOCH.sub.3 " "      87 " " NHCOCH(CH.sub.3).sub.2 "      ##STR30##      " "  88 " " NHCOC.sub.6 H.sub.11 " CH.sub.2 CH.sub.2 OH " " 89 " "     NHCOCH.sub.3 CH.sub.3 H C.sub.2 H.sub.5 " 90 " " NHCOC.sub.6 H.sub.5 " "     CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 " 91 " " NHCOCH.sub.2 OCH.sub.3 H     C.sub.2 H.sub.5 C.sub.2 H.sub.5 " 92 " " NHCOCH.sub. 2 OC.sub.6 H.sub.5     " " " " 93 " " NHCOCH.sub.2 C.sub.6 H.sub.5 " " " " 94 " " NHSO.sub.2     CH.sub.3 " " " " 95 " " NHCO.sub.2 C.sub.2 H.sub.5 " " " " 96 " C.sub.4     H.sub.9n NHCOCH.sub.3 " " " " 97 " CH.sub.2 OC.sub.6 H.sub.5 " " " " "     98 " CH.sub.2 CH.sub.2 OCH.sub.3 " " " " " 99 " C.sub.6 H.sub.5 " "     CH.sub.2 CH.sub.2 CONH.sub.2 " " 100 " " " " CH.sub.2 CH.sub.2 OC.sub.6     H.sub.5 " " 101 " " " " CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 " "  102 " "     " "      ##STR31##      " "  103 " " " " CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OCH.sub.3 " " 104 " "     " " CH.sub.2 CH(OCOCH.sub.3)CH.sub.2      OCOCH.sub.3 " "

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. Azo compounds of the formula: ##STR32## wherein R is loweralkyl or phenyl; X is O or S; R₁ is selected from lower alkyl,cyclohexyl, and phenyl wherein said lower alkyl is unsubstituted orsubstituted with 1-3 of --OH, Cl, Br, aryl, aryloxy, lower alkanoyloxy,lower alkoxy, or lower alkoxy substituted with --OH, Cl, Br, or loweralkoxy, and wherein said phenyl is unsubstituted or substituted with Cl,Br, lower alkoxy, or lower alkyl, and when X is S, R₁ is furtherselected from pyridyl, pryimidinyl, benzothiazolyl, benzoxazolyl,benzimidazolyl, azolyl radicals having the formula ##STR33## wherein Yis an oxygen or sulfur atom and Z is an ethylenically unsaturated groupof two carbon atoms or of a nitrogen and a carbon atom, wherein saidazolyl radicals may be substituted with lower alkyl, phenyl, or phenylsubstituted as above for R₁ ; R₂ is selected from hydrogen, lower alkyl,lower alkoxy, formamido, lower alkoxycarbonylamino, lower alkanoylamino,lower alkanoylamino substituted with cyano, lower alkoxy, loweralkoxycarbonyl, phenoxy, or phenyl, phenoxy, halogen substitutedphenoxy, cycloalkylcarbonyl, and lower alkylsulfonyl; R₃ is H, or loweralkyl; and R₄ and R₅ are independently selected from H, alkyl of 1-8carbons, cyclohexyl, phenyl, lower alkoxycarbonyl substituted phenyl,and lower alkyl substituted with cyclohexyl, lower alkanoyloxy, loweralkoxycarbonyl, succinimido, lower alkanoylamino, loweralkylsulfonylamino, lower alkyl sulfonyl, sulfamoyl, carbamoyl, hydroxy,pyrrolidono, phthalimido, aryl, cyano, aryloxy, lower alkoxycarbonyloxy,lower alkoxy, phenoxy, or lower alkoxyalkoxy.
 2. A compound of claim 1having the formula ##STR34##
 3. A compound of claim 1 having the formula##STR35##
 4. A compound of claim 1 having the formula ##STR36##
 5. Acompund of claim 1 having the formula ##STR37##
 6. A compound of claim 1having the formula ##STR38##